Blowing agent compositions of hydrofluoroolefins and hydrochlorofluoroolefins

ABSTRACT

The present invention relates to blowing agent compositions comprising (1) at least one hydrofluoroolefin (HFO) and (2) at least one hydrochlorofluoroolefin (HCFO) used in the preparation of foamable thermoplastic compositions. The HFOs of component (1) include, but are not limited too, 3,3,3-trifluoropropene (HFO-1243zf), 1,2,3,3,3-pentafluoropropene (HFO-1225ye), cis- and/or trans-1,3,3,3-tetrafluoropropene (HFO-1234ze), and 2,3,3,3-tetrafluoropropene (HFO 1234yf), and mixtures thereof. The HCFOs of component (2) include, but are not limited to, 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) and mixtures thereof. The blowing agent compositions are useful in the production of low density insulating foams with improved k-factor.

SUMMARY OF INVENTION

The present invention relates to blowing agent compositions comprising (1) at least one hydrofluoroolefin (HFO) and (2) at least one hydrochlorofluoroolefin (HCFO) used in the preparation of foamable thermoplastic compositions. The HFOs of component (1) include, but are not limited too, 3,3,3-trifluoropropene (HFO-1243zf), 1,2,3,3,3-pentafluoropropene (HFO-1225ye), cis- and/or trans-1,3,3,3-tetrafluoropropene (HFO-1234ze), and 2,3,3,3-tetrafluoropropene (HFO 1234yf), and mixtures thereof. The HCFOs of component (2) include, but are not limited to, 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), dichlorofluorinated propenes, and mixtures thereof. The blowing agent compositions are useful in the production of low density insulating foams with improved k-factor.

BACKGROUND OF INVENTION

With the continued concern over global climate change there is an increasing need to develop technologies to replace those with high ozone depletion potential (ODP) and high global warming potential (GWP). Though hydrofluorocarbons (HFC), being non-ozone depleting compounds, have been identified as alternative blowing agents to chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) in the production of thermoplastic foams, they still tend to have significant GWP.

Hydrofloroolefins, such as HFO-1243zf, (cis/trans)-HFO-1234ze, HFO-1234yf, and (E/Z)-HFO-1225ye, have been identified as potential low GWP blowing agents for the production of thermoplastic foams, including extruded polystyrene foams for thermal insulation.

It was discovered that blowing agent compositions comprising at least one hydrofluorolefin with at least one hydrochlorofluoroolefin can permit the production of lower density, closed-cell foam with good k-factor which will be particularly useful for thermal insulating foams. This invention may also permit the production of low density, closed-cell foams with enlarged, controlled cell size.

WO 2004/037913, WO 2007/002703, and US Pat. Publication 2004/119047 disclose blowing agents comprising halogenated alkenes of generic formula that would include numerous HFOs and HCFOs, among many other materials including brominated and iodinated compounds. The specific combination of HFOs with HCFOs in blowing agent compositions is not disclosed. Specific examples are shown for blowing agent compositions for foaming polystyrene comprising HFOs, specifically HFO-1234ze and HFO-1234yf, either alone or in combination with an HFC, and blowing agent compositions for PUR foaming comprising HCFO-1233zd. No examples of blowing agents combinations comprising HFOs and HCFOs are disclosed.

GB 950,876 discloses a process for the production of polyurethane foams. It discloses that any suitable halogenated saturated or unsaturated hydrocarbon having a boiling point below 150° C., preferably below 50° C., can be used as the blowing agent. Trichlorofluoroethene, chlorotrifluoroethene, and 1,1-dichloro-2,2-difluoroethene are disclosed in a list of suitable blowing agents along with 3,3,3-trifluoropropene. Hydrochlorofluoropropenes are not specifically disclosed nor are longer chain HCFOs nor other HFOs besides 3,3,3-trifluoropropene. There is no disclosure related to blowing agents for thermoplastic foaming, nor are the benefits of HCFOs in thermoplastic foaming mentioned, nor are the benefits of blowing agent combinations comprising HCFOs and HFOs.

CA 2016328 discloses a process for preparing closed-cell, polyisocyanate foam. Disclosed are organic compound blowing agents including halogenated alkanes and alkenes, where the alkene is propylene, and the halogenated hydrocarbons can be chlorofluorocarbons. Among the many exemplary compounds listed are specific chlorofluoroethylenes containing 1 chlorine and from 1 to 3 fluorines along with specific pentafluoropropene, tetrafluoropropene, and difluoropropene. Hydrochlorofluoropropenes are not specifically disclosed nor are longer chain HCFOs. There is no disclosure related to blowing agents for thermoplastic foaming, nor are the benefits of HCFOs in thermoplastic foaming mentioned, nor are the benefits of blowing agent combinations comprising HCFOs and HFOs.

DETAILED DESCRIPTION OF INVENTION

The present invention relates to the use of blowing agents with negligible ozone-depletion and low GWP comprising (1) at least one hydrofluoroolefin (HFO) and (2) at least on hydrochlorofluoroolefin (HCFO). The present invention discloses blowing agent and foamable resin compositions useful for the production of foams with decreased density and improved k-factor that can be used as insulating foams. In a preferred embodiment of this invention the HFO in component (1) is 3,3,3-trifluoropropene (HFO-1243zf); (cis and/or trans)-1,3,3,3-tetrafluoropropene (HFO-1234ze), particularly the trans isomer; 2,3,3,3-tetrafluoropropene (HFO-1234yf); (cis and/or trans)-1,2,3,3,3-pentafluoropropene (HFO-1225ye) and mixtures thereof. The HCFO of component (2) is preferably (cis and/or trans)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), particularly the trans isomer, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 1,1-dicloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, and mixtures thereof.

Another embodiment of this invention are foamable resin compositions containing greater than about 1 parts per hundred (pph) and less than about 100 pph of the blowing agent composition with respect to resin, preferably greater than about 2 pph and less than about 40 pph, more preferably greater than about 3 pph and less than about 25 pph, and even more preferably greater than about 4 pph and less than about 15 pph of the blowing agent composition with respect to resin.

The process for preparing a foamed thermoplastic product is as follows: Prepare a foamable polymer composition by blending together components comprising foamable polymer composition in any order. Typically, prepare a foamable polymer composition by plasticizing a polymer resin and then blending in components of a blowing agent composition at an initial pressure. A common process of plasticizing a polymer resin is heat plasticization, which involves heating a polymer resin enough to soften it sufficiently to blend in a blowing agent composition. Generally, heat plasticization involves heating a thermoplastic polymer resin near or above its glass transition temperature (Tg), or melt temperature (Tm) for crystalline polymers.

A foamable polymer composition can contain additional additives such as nucleating agents, cell-controlling agents, dyes, pigments, fillers, antioxidants, extrusion aids, stabilizing agents, antistatic agents, fire retardants, IR attenuating agents and thermally insulating additives. Nucleating agents include, among others, materials such as talc, calcium carbonate, sodium benzoate, and chemical blowing agents such azodicarbonamide or sodium bicarbonate and citric acid. IR attenuating agents and thermally insulating additives can include carbon black, graphite, silicon dioxide, metal flake or powder, among others. Flame retardants can include, among others, brominated materials such as hexabromocyclodecane and polybrominated biphenyl ether.

Foam preparation processes of the present invention include batch, semi-batch, and continuous processes. Batch processes involve preparation of at least one portion of the foamable polymer composition in a storable state and then using that portion of foamable polymer composition at some future point in time to prepare a foam.

A semi-batch process involves preparing at least a portion of a foamable polymer composition and intermittently expanding that foamable polymer composition into a foam all in a single process. For example, U.S. Pat. No. 4,323,528, herein incorporated by reference, discloses a process for making polyolefin foams via an accumulating extrusion process. The process comprises: 1) mixing a thermoplastic material and a blowing agent composition to form a foamable polymer composition; 2) extruding the foamable polymer composition into a holding zone maintained at a temperature and pressure which does not allow the foamable polymer composition to foam; the holding zone has a die defining an orifice opening into a zone of lower pressure at which the foamable polymer composition foams and an openable gate closing the die orifice; 3) periodically opening the gate while substantially concurrently applying mechanical pressure by means of a movable ram on the foamable polymer composition to eject it from the holding zone through the die orifice into the zone of lower pressure, and 4) allowing the ejected foamable polymer composition to expand to form the foam.

A continuous process involves forming a foamable polymer composition and then expanding that foamable polymer composition in a non-stop manner. For example, prepare a foamable polymer composition in an extruder by heating a polymer resin to form a molten resin, blending into the molten resin a blowing agent composition at an initial pressure to form a foamable polymer composition, and then extruding that foamable polymer composition through a die into a zone at a foaming pressure and allowing the foamable polymer composition to expand into a foam. Desirably, cool the foamable polymer composition after addition of the blowing agent and prior to extruding through the die in order to optimize foam properties. Cool the foamable polymer composition, for example, with heat exchangers.

Foams of the present invention can be of any form imaginable including sheet, plank, rod, tube, beads, or any combination thereof. Included in the present invention are laminate foams that comprise multiple distinguishable longitudinal foam members that are bound to one another.

EXAMPLES Examples 1-8 Solubility and Diffusivity of Gases in Polystyrene

The solubility and diffusivity of gases in polystyrene resin was measured using capillary column inverse gas chromatography (cc-IGC) as described in: Hadj Romdhane, Ilyess (1994) “Polymer-Solvent Diffusion and Equilibrium Parameters by Inverse Gas-Liquid Chromatography” PhD Dissertation, Dept. of Chem. Eng., Penn State University. and Hong S U, Albouy A, Duda J L (1999) “Measurement and Prediction of Blowing Agent Solubility in Polystyrene at Supercritical Conditions” Cell Polym 18(5):301-313.

A 15m long, 0.53 mm diameter GC capillary-column was prepared with a 3 micron thick polystyrene internal film coating. The column was installed into a Hewlet Packard 5890 Series II Gas Chromatograph with flame ionizer detector. Elution profiles for gases being tested were analyzed according the method outlined in the reference, using methane as the reference gas. The results give the diffusion coefficient of the gas through the polymer, Dp, and the solubility of the gas in the polymer in terms of the partition coefficient, K, which is the ratio of the concentration of the gas in the polymer phase to the concentration in the vapor phase. As such, the greater the value of K for a particular gas in the resin the greater its solubility in that resin.

Table 1 shows the partition coefficient and diffusivity values for several gases in polystyrene at 140° C. Comparative examples 1 and 2 show the solubility and diffusivity of two well studied blowing agents in polystyrene: HCFC-142b (1-chloro-1,1-difluoroethane) and HFC-134a (1,1,1,2-tetrafluoroethane). Examples 3-6 show the solubility and diffusivity of selected HFOs in polystyrene: HFO-1243zf (3,3,3-trifluoropropene), HFO-1234ze (1,3,3,3-tetrafluoropropene), HFO-1234yf (2,3,3,3-tetrafluoropropene), HFO-1225ye (1,2,3,3,3-pentafluoropropene). Examples 7 and 8 show the solubility and diffusivity of trans-HCFO-1233zd (1-chloro-3,3,3-trifluoropropene) and HCFO-1233xf (2-chloro-3,3,3-trifluoropropene),

The good solubility and favorable diffusivity of the HCFOs in polystyrene indicate that they should be effective coblowing agents and/or processing aids for the production of thermoplastic foams using HFO blowing agents. The solubility of the HCFOs in polystyrene is sufficient to provide useful plasticization of the thermoplastic resin to assist in foaming. As can be seen, HCFO-1233xf has a solubility in polystyrene comparable to that of HCFC-142b.

TABLE 1 Partition Coefficient and Diffusivity of Gases in Polystyrene at 140° C. by Inverse Gas Chromatography Bp Mw Dp Example Gas (° C.) (g/mol) K (cm²/s) 1 HCFC-142b −9.8 100.49 1.249 2.61E−08 2 HFC-134a −26.1 102.02 0.397 3.40E−08 3 HFO-1243zf −22 96.05 0.544 2.95E−08 4 HFO-1234ze −16 114.04 0.423 3.09E−08 5 HFO-1225ye −18 132.03 0.312 2.44E−08 6 HFO-1234yf −28.5 114.04 0.275   >2E−08 7 HCFO-1233zd 20.5 130.5 2.326 1.72E−08 8 HCFO-1233xf 15 130.5 1.475 1.67E−08

Examples 9-18

Extruded polystyrene foam was produced using a counter-rotating twin screw extruder with internal barrel diameters or 27 mm and a barrel length of 40 diameters. The screw design was suitable for foaming applications. The pressure in the extruder barrel was controlled with the gear pump and was set high enough such that the blowing agent dissolved in the extruder. The extruder die for examples 10-18 was an adjustable-lip slot die with a gap width of 6.35 mm. For example 1, the die was a 2 mm diameter strand die with a 1 mm land length. Two grades of general purpose polystyrene were used for the extrusion trials and fed to the extruder at rates of either 2.27 or 4.54 kg/hr (5 or 10 lb/hr). Blowing agents were pumped into the polystyrene resin melt at a controlled rate using high pressure delivery pumps. In the extruder, the blowing agent is mixed and dissolved in the resin melt to produce an expandable resin composition. The expandable resin composition is cooled to an appropriate foaming temperature and then extruded from the die where the drop in pressure initiates foaming. Talc was used as a nucleating agent and was pre-blended with polystyrene to make a masterbatch of 50 wt % talc in polystyrene. Beads of this masterbatch were mixed with polystyrene pellets to achieve 0.5 wt % talc in each experiment.

The density, open cell content, and cell size was measured for foam samples collected during each run. Density was measured according to ASTM D792, open cell content was measured using gas pychnometry according to ASTM D285-C, and cell size was measured by averaging the cell diameters from scanning electron microscope (SEM) micrographs of foam sample fracture surfaces. SEM images are also used to observe the cell structure and qualitatively check for open cell content.

Table 2 shows data for examples 9 through 14, including the loading of each blowing agent in the formulation, the resin feed rate, melt flow index of the resin, the expandable resin melt temperature, and the density, cell size, and open cell content of the resulting foamed product.

Comparative example 9 is typical for polystyrene foaming with HFC-134a, where the poor solubility and difficulties in processing tend to lead to higher density foam with smaller size and more open cells.

Comparative examples 10 through 12 show results for foaming with 3,3,3-trifluoropene (HFO-1243zf; TFP). At a loading of 8.5 wt % TFP the resulting foam had smaller cell size while comparative density to examples 10 and 11.

In examples 13 and 14, blowing agent compositions of TFP (HFO-1243zf) and HCFO-1233zd permitted production of lower density foam than achievable with TFP alone along with a beneficial enlargement in the cell size, where it was possible to produce closed-cell foam product with cell sizes greater than 0.2 mm at densities less than 53 kg/m³. These foams would be useful as thermal insulating foams with improved k-factor. The HCFO-1233zd was predominantly the trans-isomer.

Examples 15 and 16 were produced during using HFO-1234yf (2,3,3,3-tetrafluoroethane) as the only blowing agent. At a loading of 5.7 wt % 1234yf, as shown in example 16, the foamed product had very small cell size, macrovoids, blowholes, high open cell content, and frequent periods of popping at the die caused by undissolved blowing agent. Increasing the content of 1234yf made these problems worse. For examples 17 and 18, blowing agent compositions of HFO-1234yf and HCFO-1233zd permitted production of lower density foam than was produced using the HFO-1234yf alone. The foamed samples of examples 17 and 18 were of good quality, with few defects and produced without popping at the die.

TABLE 2 Blowing Agent Loading Polystyrene Resin Foam Properties 134a TFP 1234yf 1233zd Feed MFI T_(melt) Density Cell Size OCC Example (wt %) (wt %) (wt %) (wt %) (kg/hr) (g/10 min) (° C.) (kg/m³) (mm) (%) 9 6.4 — — — 2.27 4.0 111 60.9 0.06 23 10 — 6.6 — — 2.27 11.0 114 57.6 0.11 <5 11 — 7.2 — — 2.27 11.0 115 56.5 0.11 <5 12 — 8.5 — — 4.54 4.0 117 58.0 0.05 <5 13 — 4.1 — 6.6 4.54 11.0 113 44.3 0.29 <5 14 — 6.5 — 3.4 4.54 11.0 113 52.5 0.35 <5 15 — — 4.4 — 4.54 11.0 117 90.9 0.15 5 16 — — 5.7 — 4.54 11.0 115 71.6 0.06 31.4 17 — — 4.2 4.3 4.54 11.0 114 55.2 0.12 <5 18 — — 4.8 5.0 4.54 11.0 113 53.5 0.08 <5

Although the invention is illustrated and described herein with reference to specific embodiments, it is not intended that the appended claims be limited to the details shown. Rather, it is expected that various modifications may be made in these details by those skilled in the art, which modifications may still be within the spirit and scope of the claimed subject matter and it is intended that these claims be construed accordingly. 

1. A blowing agent composition for thermoplastic foaming comprising (1) at least one hydrofluoroolefin and (2) at least one hydrochlorofluoroolefin.
 2. The blowing agent composition of claim 1 comprising about 2 wt % to about 90 wt % of said (2) at least one hydrochlorofluoroolefin.
 3. The blowing agent composition of claim 1 comprising about 5 wt % to about 80 wt % of said (2) at least one hydrochlorofluoroolefin.
 4. The blowing agent composition of claim 1 comprising about 10 wt % to about 70 wt % of said (2) at least one hydrochlorofluoroolefin.
 5. The blowing agent composition of claim 1 comprising about 20 wt % to about 65 wt % of said (2) at least one hydrochlorofluoroolefin.
 6. The blowing agent composition of claim 1 comprising about 30 wt % to about 60 wt % of said (2) at least one hydrochlorofluoroolefin.
 7. The blowing agent composition of claim 1 further comprising a hydrofluorocarbon, alkane, carbon dioxide, methyl formate, inert gas, atmospheric gas, alcohol, ether, fluorinated ether, unsaturated fluorinated ether, ketone, fluoroketone, water, and mixtures thereof
 8. The blowing agent composition of claim 1 wherein said hydrofluoroolefin is selected from C3 through C5 fluorinated alkene or mixtures thereof.
 9. The blowing agent composition of claim 8 wherein said C3 through C5 fluorinated alkene is selected from trifluoropropene, tetrafluoropropene, pentafluoropropene, or mixtures thereof.
 10. The bowing agent composition of claim 9 wherein said trifluoropropene is 3,3,3-trifluoropropene.
 11. The blowing agent composition of claim 9 wherein said tetrafluoropropene is selected from cis-1,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, or mixtures thereof.
 12. The blowing agent composition of claim 9 where the pentafluoropropene is E-1,2,3,3,3-pentafluoropropene, Z-1,2,3,3,3-pentafluoropropene, and mixtures thereof.
 13. The blowing agent composition of claim 1 wherein said hydrochlorofluoroolefin contains three or more carbons atoms.
 14. The blowing agent composition of claim 1 wherein said hydrochlorofluoroolefin is selected from 1-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, or mixtures thereof.
 15. The blowing agent composition of claim 14 where said 1-chloro-3,3,3-trifluoropropene comprises greater than 75% of the trans-isomer.
 16. The blowing agent composition of claim 7 wherein said hydrofluorocarbon is selected from HFC-32, HFC-161, HFC-152, HFC-152a, HFC-143, HFC-143a, HFC-134, HFC-134a, HFC-125, HFC-245fa, HFC-365mfc, HFC-227ea, or mixtures thereof.
 17. The blowing agent composition of claim 16 wherein said hydrofluorocarbon is selected from HFC-134a, HFC-152a, HFC-32, HFC-143a, HFC-245fa, or mixtures thereof.
 18. The blowing agent composition of claim 7 wherein said alkane is selected from propane, butane, pentane, or hexane.
 19. The blowing agent composition of claim 18 wherein said pentane is selected from n-pentane, cyclopentane, iso-pentane or mixtures thereof.
 20. The blowing agent composition of claim 7 wherein said alcohol is selected from ethanol, iso-propanol, butanol, ethyl hexanol, methanol, or mixtures thereof.
 21. The blowing agent composition of claim 7 wherein said ether is selected from dimethyl ether, diethyl ether, methylethyl ether, or mixtures thereof.
 22. The blowing agent composition of claim 7 wherein said ketone is selected from acetone, methyl ethyl ketone, or mixtures thereof.
 23. The blowing agent composition for thermoplastic foam of claim 1 wherein said thermoplastic is selected from polystyrene, polyethylene, polypropylene, or mixtures thereof.
 24. A foamable resin composition comprising a thermoplastic resin and a blowing agent comprising (1) at least one hydrofluoroolefin and (2) at least one hydrochlorofiuoroolefin.
 25. The foamable resin composition of claim 24 wherein said thermoplastic resin is selected from polystyrene, polyethylene, polypropylene, or mixtures thereof.
 26. The foamable resin composition of claim 24 comprising less than about 100 pph of said blowing agent with respect to said thermoplastic resin.
 27. The foamable resin composition of claim 24 comprising from about 1 pph to about 100 pph of said blowing agent with respect to said thermoplastic resin.
 28. The foamable resin composition of claim 24 comprising from about 2 pph to about 40 pph of said blowing agent with respect to said thermoplastic resin.
 29. The foamable resin composition of claim 24 comprising from about 3 pph to about 25 pph of said blowing agent with respect to said thermoplastic resin.
 30. The foamable resin composition of claim 24 comprising from about 4 pph to about 15 pph of said blowing agent with respect to said thermoplastic resin.
 31. The blowing agent composition of claim 1 further comprising dyes, pigments, cell-controlling agents, fillers, antioxidants, extrusion aids, stabilizing agents, antistatic agents, fire retardants, IR attenuating agents, thermally insulating additives, plasticizers, viscosity modifiers, impact modifiers, gas barrier resins, carbon black, surfactants, and mixtures thereof.
 32. A foamed product produced using the blowing agent composition of claim 1
 33. A process for producing the foamed product of claim
 32. 